Process for cleaving dichloroisopropyl ether

ABSTRACT

Process for the acidolysis or ether cleavage of dichloroisopropyl ether to convert it into propylene dichloride and propylene chlorohydrin by the steps of adding a catalytic amount of zinc chloride, aluminum chloride or ferric chloride to the dichloroisopropyl ether, heating the mixture in an atmosphere of hydrogen chloride gas, and recovering the products. The process is useful to convert waste streams containing dichloroisopropyl ether into valuable products.

United States Patent H 1 OTHER PUBLICATIONS Fried et al., J. Am. Chem. Soc., 63, 2691, 1941 Roberts, Jr. [451 Mar. 27, 1973 PROCESS FOR CLEAVING Starr et al., I. Am. Chem. Soc., 56, 1595-1596, 1934 DICHLOROISOPROPYL ETHER Burwell, Chem. Reviews 54, 622-630, 654-656, 1954 [75] Inventor: Reginald F. Roberts, Jr., Baton Primary Examiner floward Mars Rouge, Attomey-William M. Yates et a].

[73] Assignee: The Dow Chemical Company,

Midland, Mich. [57] ABSTRACT [22] Filed: Oct 22 1971 Procees for the acidolysis or ether cleavage of dichloroisopropyl ether to convert it into propylene- [211 App]. No.: 191,631 dichloride and propylene chlorohydrin by the steps of adding a catalytic amount of zinc chloride, aluminum chloride or ferric chloride to the dichloroisopropyl [52] US. Cl. ..260/633, 260/652 R ether, heating the mixture in an atmosphere of [51] Int. Cl ..C07c 31/34 hydrogen chloride gas, and recovering the products Fleld of Search R The process is useful to convert waste Streams conv taining dichloroisopropyl ether into valuable products. [56] References Cited 3 Claims, No Drawings PROCESS FOR CLEAVING DICI'ILOROISOPROPYL ETIIER BACKGROUND OF THE INVENTION This invention relates to a process for the conversion of a waste stream containing dichloroisopropyl ether (DCIPE) into valuable products. More particularly, the invention concerns the acidolysis or ether-cleavage of a waste feedstock containing DCIPE into propylene chlorohydrin (PCH) and 1,2-dichloropropane (PDC).

Dichloroisopropyl ether or bis(ch1oroisopropy1)ether is a by-product in the commercial production of propylene glycol by the liquid-phase reaction of chlorine, water and propylene. See, for example, Encyclopedia of Chemical Technology, Second Edition, Vol. 16, pages 600-609 (1968). Because DCIPE is a long-lasting pollutant and has to be disposed of by incineration or by burial in the ground, it became increasingly important that an economic means be found to dispose of or convert the vast amounts of this by-product which are created.

It is known from thearticle by Fried et al., J. Am. Chem. Soc., 63,2691 (1944) that tetrahydrofuran can be cleaved to tetramethylene chloride using gaseous hydrogen chloride and large amounts i.e., 50percent by weight). of zinc chloride. In the present invention only catalytic amounts (less than 2 percent by weight) of zinc chloride are used to effect cleavage.

SUMMARY OF THE INVENTION It now has been discovered that waste streams containing DCIPE from the production of propylene glycol minum chloride or ferric chloride under an atmosphere of hydrogen chloride to produce PCH and PDC.

In accordance with this invention there is provided a process for the recovery of useful chlorinated products from the acidolysis of a waste-stream feedstock, containing a major proportion of DCIPE and a minor proportion of PDC with or without a small amount of PCH. The steps of the process generally comprise the steps of: (a) adding a catalytic amount of zinc chloride, aluminum chloride or ferric chloride to the feedstock; (b) heating this mixture in a reaction zone under an atmosphere of hydrogen-chloride gas to a temperature in the range from about 150 to about 240 C under a pressure of from about zero to about 225 pounds per square inch gage (psig); and (c) recovering chlorinated products. Since the products of the process comprise mainly PDC and PCH, these are distilled off from the other products to recover them in a high yield.

DETAILED DESCRIPTION tion in acetone, DCIPE, or other inert organic liquids.

Generally, the waste stream will vary from about 60 percent to about percent by weight of DCIPE, with the remainder being PDC and about 0-5 percent PCH.

For the purposes of this invention, a catalytic amount of the above Lewis acids is defined as about 0.01 to about 1.0 weight percent based on the feed. The preferred amount is from 0.05 to 0.2 percent.

This mixture is then pumped into a corrosion-resistant, pressured reactor such as stainless steel, a nickel-jacketed reactor, Monel, or the like wherein the contents are heated (e.g., steam coils or the like) to a temperature in the range from about to about 240C. Preferably the temperature range is from about to about 220C.

The heating step is carried out in an atmosphere of hydrogen-chloride gas under a pressure of 0-225 psig, but preferably in the range from 10-50 psig.

It is desirable to provide a continuous purge or flow rate of hydrogen chloride. Generally this flow rate will be from about 0.1 to about 1.0 pounds and preferably from about 0.21 to about 0.5 pounds of I-ICI per pound of feedstock.

The vaporized products of the reaction are continuously removed overhead and fractionally distilled to recover the desired PDC and PCI-I from the propionaldehyde and chloropropenes which are also formed. The non-volatible reaction products such as 1,2,3- trichloropropane, polymers, and the Lewis acid used are removed periodically from the bottom of the reactor for incineration or other disposal means. If desired,

theunreacted DCIPE can be continuously recycled to EXAMPLE 1 Into a Monel reactor of approximately 190 ml capacity .was charged:

104.0 grams (0.608 mole) of reagent grade (97 percent) dichloroisopropyl ether (DCIPE) 0.20 gm (0.0015 mole, 0.2 pph) of anhydrous ZnCl The reactor was sealed by closing a valve. Stirring was begun by actuating an electrically-driven shaft connected to a propeller-type agitator. The steam-jacketed reactor and contents were heated to approximately C with 50-100 psig steam, and reaction was initiated by pressuring in anhydrous HCI (from a cylindrical metal bomb through a pressure regulator) to a total pressure of about 150 psig. The reaction was continued at essentially constant temperature and pressure (with I-ICl supplied as needed to maintain pressure) for a period of 6 hours. At the end of this time, the reaction was stopped by closing the 1-1Cl inlet valve, shutting off the steam, and sending cooling water through the reactor jacket. When the reaction mixture had cooled to approximately 30-40C, the reactor was vented down to atmospheric pressure and the product recovered by opening a valve. The product mixture was found to contain 5 percent propylene dichloride (PDC), 4 percent propylene chlorohydrin (PCH), and 91 percent unreacted ether (DCIPE) by weight. The total weight of the recovered product mixture was 105.9 grams, and the total weight of ether and zinc chloride charged was 104.2 grams. The calculated amount of I-ICI reacted was 1.7 grams. Recovery was, therefore, essentially quantitative. The amount of ether which reacted was 0.045 moles or 4.4 percent; of the ether which reacted, 0.047 moles or 52 percent was converted to 1,2- dichloropropane (PDC), and 0.044 moles or 48 percent to propylene chlorohydrin (PCl-l EXAMPLE 2 Dichloroisopropyl ether (DCIPE) containing 16 percent PDC and percent PCl-l was reacted with anhydrous hydrogen chloride in a 1 liter stainless steel reactor. The catalystused was ZnCl at a concentration of 0.002 'g. ZnCl /g. DCIPE. The reactor was heated with electric-strip heaters to the reaction temperature of 200C which was controlled by a temperature controller. The HCl was fed from a cylinder at the rate of 0.72 g. HCl/min., which was flow-controlled with a control valve. The reactor pressure (measured by a pressure transmitter) was controlled at 50 psig with a control valve in the vapor-take-off line. The reactor was initially charged with 500 g. of DClPE, which comprised half the reactor volume. The liquid level in the reactor was measured by a differential-pressure cell, and maintained at 50 percent of the reactor volume. As the level dropped off, the ether-feed-control valve opened, allowing more DCIPE to be fed from a cylinder mounted on a scale. The cylinder weight was recorded periodically to obtain an ether feed rate. The vaporized products were taken off, condensed, and collected in two sample scrubbers. These were packed, one with ice and one with dry ice. The HCl was scrubbed with water. The product rate was obtained by weighting the amount'of product collected in the sam ple scrubbers. The HCl in the scrubber was measured by titration. At these reaction conditions, an ether-feed rate of 1.0 gm/min. was used and a product rate of 1.24 gm/min. was obtained. A gas chromatograph was used to analyze the ether feed and the product samples. Calculations were based on line-out or steady-state conditions. For these reaction conditions a conversion of 88.3 percent was obtained. The yield to PDC was 44.8 percent and the yield to PCH was 35.9 percent, giving a total yield to the desired products (PDC and PCH) of 80.7 percent. The volume-conversion-rate was 0.687 lb/hr. gal. The byproducts formed were of two types: lights (acetone, propionaldehyde, chloropropenes), and heavies, non-volatile matter (NVM) such as polymeric residues, and 1,2,3-trichloropropane.

Similarly good conversions were obtained with other DCIPE waste streams containing varing amounts of PDC and PCl-l.

The process has also been operated with an aluminum-chloride or ferric-chloride catalyst, with somewhat less yield and conversion. Other Lewis-acid catalysts such as zinc bromide have been tried; but they are economically less attractive, in that the increased cost does not result in commensurately increased yields.

lclaim:

1. A process for the recovery of chlorinated products from the acidcleavage of a waste feedstock containing a major proportion of dichloroisop'ropyl ether and a minor proportion of propylene dichloride, which comprises the steps of: l

A. adding a catalytic amount of zinc chloride, aluminum chloride or ferric chloride to the feedstock to form a mixture therewith; B. heating said mixture in a reaction zone under an atmosphere of hydrogen-chloride gas to a temperature in the range from about to'about 240C under a pressure from about zero to about 225 psig; and

C. recovering chlorinated products therefrom.

2. A process as set forth in claim 1, whereinpropylene dichloride and propylene chlorohydrin ar separately recovered by distillation.

3. A process as set forth in claim 1 wherein zinc chloride is used as catalyst. 

2. A process as set forth in claim 1, wherein propylene dichloride and propylene chlorohydrin are separately recovered by distillation.
 3. A process as set forth in claim 1 wherein zinc chloride is used as catalyst. 